JP4451643B2 - Surface material for hot carpet and manufacturing method thereof - Google Patents
Surface material for hot carpet and manufacturing method thereof Download PDFInfo
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- JP4451643B2 JP4451643B2 JP2003394983A JP2003394983A JP4451643B2 JP 4451643 B2 JP4451643 B2 JP 4451643B2 JP 2003394983 A JP2003394983 A JP 2003394983A JP 2003394983 A JP2003394983 A JP 2003394983A JP 4451643 B2 JP4451643 B2 JP 4451643B2
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- 239000000463 material Substances 0.000 title claims description 50
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229920005989 resin Polymers 0.000 claims description 48
- 239000011347 resin Substances 0.000 claims description 48
- 239000006260 foam Substances 0.000 claims description 28
- 238000007639 printing Methods 0.000 claims description 22
- 229920000573 polyethylene Polymers 0.000 claims description 21
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 19
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 238000005187 foaming Methods 0.000 claims description 13
- 239000004088 foaming agent Substances 0.000 claims description 8
- 238000010030 laminating Methods 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000012968 metallocene catalyst Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- 239000005038 ethylene vinyl acetate Substances 0.000 description 8
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 8
- -1 polyethylene Polymers 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
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- 239000004156 Azodicarbonamide Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004278 EU approved seasoning Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
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- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 2
- 235000019399 azodicarbonamide Nutrition 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 2
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 2
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 2
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
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- 238000007646 gravure printing Methods 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
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- 239000004702 low-density polyethylene Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
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- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000003851 corona treatment Methods 0.000 description 1
- 238000009429 electrical wiring Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 239000005043 ethylene-methyl acrylate Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- ALIFPGGMJDWMJH-UHFFFAOYSA-N n-phenyldiazenylaniline Chemical compound C=1C=CC=CC=1NN=NC1=CC=CC=C1 ALIFPGGMJDWMJH-UHFFFAOYSA-N 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
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- 239000003973 paint Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
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- 239000010703 silicon Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
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Landscapes
- Carpets (AREA)
- Laminated Bodies (AREA)
Description
本発明は、特に表面についた汚れの除去が容易で、かつ耐熱性や柔軟性に優れるホットカーペット用表面材、およびその製造方法に関する。 The present invention relates to a surface material for a hot carpet that is particularly easy to remove stains on the surface and has excellent heat resistance and flexibility, and a method for producing the same.
従来よりホットカーペット用表面材としては、保温性、意匠性に優れるという観点から、表面が繊維素材よりなるものが一般的に使用されているが、特にキッチンやダイニングなどにおいて、食物、飲料、調味料などをこぼすことなどによる汚れの除去を容易にするために、近年、表面が合成樹脂製であるホットカーペット用表面材が提案されている（例えば、特開２０００−２９７９４４号公報）。 Conventionally, as surface materials for hot carpets, those made of fiber materials are generally used from the viewpoint of excellent heat retention and design, but food, beverages, seasonings are particularly used in kitchens and dining areas. In recent years, a surface material for a hot carpet whose surface is made of a synthetic resin has been proposed in order to facilitate removal of dirt caused by spilling a material or the like (for example, JP 2000-297944 A).
上記のようなホットカーペット用表面材として、成形加工性や意匠付与性などに優れることから、塩化ビニル樹脂からなる表面材なども提案されているが、火災の際などにおける低温での燃焼時に有毒ガスを発生する虞れがあることや、昨今の地球環境保全の観点から、塩化ビニル樹脂から他の素材への代替の市場要求が強くなってきている。
しかし、例えば上記の特開２０００−２９７９４４号公報に記載される電気カーペット用表皮材に用いられるポリエチレンなどの合成樹脂は、耐熱性が十分でないため、ホットカーペット上に表面材として使用するなど、常に熱のかかる状態においては、変形が起こるなどの問題がある。
耐熱性を追求する場合、ポリプロピレン樹脂や高密度ポリエチレン樹脂などの材料を使用することが考えられているが、これらの樹脂は、柔軟性に乏しいという問題を有している。
However, for example, a synthetic resin such as polyethylene used for an electric carpet skin material described in JP-A-2000-297944 is not sufficient in heat resistance, so that it is always used as a surface material on a hot carpet. In a state where heat is applied, there are problems such as deformation.
When pursuing heat resistance, it is considered to use a material such as polypropylene resin or high-density polyethylene resin, but these resins have a problem of poor flexibility.
本発明は、防汚性に優れ、かつ耐熱性、および柔軟性に優れるホットカーペット用表面材、およびその製造方法を提供することを課題とする。 This invention makes it a subject to provide the surface material for hot carpets which is excellent in antifouling property, and is excellent in heat resistance and a softness | flexibility, and its manufacturing method.
本発明者らは、上記の課題を解決するために検討を行った結果、ホットカーペット用表面材に発泡層を設け、これを構成する樹脂を、水添スチレン・ブタジエン共重合体とエチレン系重合体の混合体として、非架橋で発泡させた層とすることにより、柔軟性を損なうことなく耐熱性に優れるホットカーペット用表面材とすることができることを見出し、本発明を完成するに至った。 As a result of investigations to solve the above-mentioned problems, the present inventors have provided a foam layer on the surface material for hot carpet, and the resin constituting the foam layer is made of a hydrogenated styrene / butadiene copolymer and an ethylene-based polymer. It has been found that by forming a non-crosslinked foamed layer as a blended mixture, a surface material for hot carpet having excellent heat resistance can be obtained without impairing flexibility, and the present invention has been completed.
すなわち、本発明は、〔１〕下から順に、基材層、発泡層、意匠印刷層、透明樹脂層が設けられてなるホットカーペット用表面材において、この発泡層が、水添スチレン・ブタジエン共重合体５０〜８０重量％とエチレン系重合体５０〜２０重量％との混合体を非架橋で発泡させた層であることを特徴とするホットカーペット用表面材をその要旨とする。
上記のエチレン系重合体は、メタロセン触媒を用いて重合されたものであってもよい。
また、本発明は、〔２〕（１）発泡剤を含有した発泡層の構成樹脂が水添スチレン・ブタジエン共重合体５０〜８０重量％とエチレン系重合体５０〜２０重量％との混合体であり非架橋かつ非発泡状態で成形して樹脂層を構成する工程、
（２）非発泡状態の樹脂層の一方の面に基材層を積層する工程、
（３）非発泡状態の樹脂層の他方の面に印刷を施して意匠印刷層を設ける工程、
（４）意匠印刷層の上面に透明樹脂層を積層する工程、
（５）加熱して非発泡状態の樹脂層を発泡成形する工程、
からなることを特徴とする上記ホットカーペット用表面材の製造方法をもその要旨とする。
That is, the present invention provides [1] a hot carpet surface material provided with a base material layer, a foam layer, a design print layer, and a transparent resin layer in this order from the bottom. The gist of the surface material for a hot carpet is a non-crosslinked foam layer of a mixture of 50 to 80% by weight of a polymer and 50 to 20% by weight of an ethylene-based polymer.
The ethylene-based polymer may be polymerized using a metallocene catalyst.
The present invention also provides [2] (1) a mixture of 50 to 80% by weight of a hydrogenated styrene / butadiene copolymer and 50 to 20% by weight of an ethylene polymer as a constituent resin of a foam layer containing a foaming agent. A step of forming a resin layer by molding in a non -crosslinked and non-foamed state,
(2) a step of laminating a base material layer on one surface of the non-foamed resin layer,
(3) A step of printing on the other surface of the non-foamed resin layer to provide a design print layer;
(4) A step of laminating a transparent resin layer on the upper surface of the design print layer,
(5) A step of foaming a non-foamed resin layer by heating,
The gist of the method for producing a surface material for a hot carpet is characterized by comprising:
本発明のホットカーペット用表面材は、最上面から下面側に順次、透明樹脂層、意匠印刷層、発泡層が積層され、最下面に基材層が積層されるという構成からなり、その発泡層が水添スチレン・ブタジエン共重合体とエチレン系重合体の混合体を非架橋で発泡させた層からなる。
従来、種々の合成樹脂製用品に柔軟性を付与するために、エチレン−酢酸ビニル共重合体（ＥＶＡ）が多用されて来ているが、ＥＶＡは、柔軟性はあるが、熱による軟化温度が低いため、本発明のホットカーペット用表面材には適していない。
もし、ＥＶＡを使用するのであれば、耐熱性を考慮して、エチレン系重合体の混合割合を増加させ、耐熱性を向上させることが考えられる。しかし、エチレン系重合体の含有量が増すと、エチレン系重合体の特性から、製品（発泡層）が硬くなり、柔軟性に欠けたものとなる。
そこで本発明では、水添スチレン・ブタジエン共重合体の耐熱性・柔軟性に優れる性能を生かし、ＥＶＡを、この水添スチレン・ブタジエン共重合体に代替させ、全体の風合いを柔軟性に富むものとしながら、耐熱性を付与するものである。
The surface material for hot carpets of the present invention comprises a structure in which a transparent resin layer, a design printing layer, and a foam layer are laminated sequentially from the uppermost surface to the lower surface side, and a base material layer is laminated on the lowermost surface. Consists of a layer obtained by foaming a mixture of a hydrogenated styrene / butadiene copolymer and an ethylene polymer in a non-crosslinked manner.
Conventionally, ethylene-vinyl acetate copolymer (EVA) has been widely used to give flexibility to various synthetic resin products, but EVA is flexible but has a softening temperature due to heat. Since it is low, it is not suitable for the surface material for hot carpet of the present invention.
If EVA is used, considering the heat resistance, it is conceivable to increase the mixing ratio of the ethylene polymer to improve the heat resistance. However, when the content of the ethylene polymer increases, the product (foamed layer) becomes hard and lacks flexibility due to the characteristics of the ethylene polymer.
Therefore, in the present invention, taking advantage of the heat resistance and flexibility of the hydrogenated styrene / butadiene copolymer, EVA is replaced with this hydrogenated styrene / butadiene copolymer, and the overall texture is rich in flexibility. However, it provides heat resistance.
水添スチレン・ブタジエン共重合体としては、水添率５０〜１００％程度、好ましくは８０〜１００％程度のものが好適に使用される。
この樹脂のスチレンとブタジエンの共重合割合は、重量比で、スチレン：ブタジエン＝１０：９０〜５０：５０程度のものが適している。
As the hydrogenated styrene / butadiene copolymer, those having a hydrogenation rate of about 50 to 100%, preferably about 80 to 100% are suitably used.
The copolymerization ratio of styrene and butadiene in this resin is preferably about styrene: butadiene = 10: 90 to 50:50 by weight.
エチレン系重合体としては、ポリエチレン（ＰＥ）や、エチレン−酢酸ビニル共重合体（ＥＶＡ）、エチレン−メチルメタクリレート共重合体（ＥＭＭＡ）、エチレン−エチルアクリレート共重合体（ＥＥＡ）、エチレン−メチルアクリレート共重合体（ＥＭＡ）、エチレン−アクリル酸共重合体（ＥＡＡ）、エチレン−メタクリル酸共重合体（ＥＭＡＡ）、アイオノマーなどのエチレン系共重合体を使用することができ、これらは、単独で用いてもよいし、適宜の組み合わせによる２種以上を混合して用いてもよい。
エチレン系重合体のうち、ポリエチレンを用いる場合は、好ましくはメタロセン触媒により実質的に線状に重合したもの、具体的には低密度ポリエチレン樹脂（ＬＤＰＥ）や線状低密度ポリエチレン樹脂（ＬＬＤＰＥ）などを用いることにより、ホットカーペット用表面材としてより相応しい柔軟性を得ることができる。
Examples of the ethylene polymer include polyethylene (PE), ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), and ethylene-methyl acrylate. An ethylene copolymer such as a copolymer (EMA), an ethylene-acrylic acid copolymer (EAA), an ethylene-methacrylic acid copolymer (EMAA), or an ionomer can be used, and these are used alone. Alternatively, two or more kinds in an appropriate combination may be mixed and used.
Among polyethylene polymers, when polyethylene is used, it is preferably polymerized substantially linearly with a metallocene catalyst, specifically low density polyethylene resin (LDPE), linear low density polyethylene resin (LLDPE), etc. By using this, it is possible to obtain more appropriate flexibility as a surface material for hot carpet.
発泡層において、水添スチレン・ブタジエン共重合体とエチレン系重合体との配合比は、水添スチレン・ブタジエン共重合体が５０〜８０重量％、好ましくは６５〜８０重量％、エチレン系重合体が５０〜２０重量％、好ましくは４５〜２０重量％が適している。
水添スチレン・ブタジエン共重合体の配合量が上記より多い（エチレン系重合体の配合量が上記より少ない）と、得られる発泡層の柔軟性が不十分となったり、成形加工性に問題を生じたりする場合があり、水添スチレン・ブタジエン共重合体が上記より少ないと（エチレン系重合体の配合量が上記より多いと）、耐熱性に問題が生じる場合がある。
In the foamed layer, the blending ratio of the hydrogenated styrene / butadiene copolymer and the ethylene polymer is 50 to 80% by weight of the hydrogenated styrene / butadiene copolymer, preferably 65 to 80% by weight, and the ethylene polymer. Is preferably 20 to 20% by weight, preferably 45 to 20% by weight.
If the amount of the hydrogenated styrene / butadiene copolymer is greater than the above (the amount of the ethylene polymer is less than the above), the resulting foamed layer will have insufficient flexibility or a problem in molding processability. If the amount of the hydrogenated styrene / butadiene copolymer is less than the above (the amount of the ethylene polymer is more than the above), there may be a problem in heat resistance.
発泡剤としては、一般に用いられているものを用いればよいが、具体例としては、Ｎ，Ｎ−ジニトロソペンタメチレンテトラミンなどのニトロソ化合物、アゾジカルボンアミド、アゾビスイソブチロニトリル、ジアゾアミノベンゼンなどのアゾ化合物、ベンゼンスルホニルヒドラジド、４，４’−オキシビス（ベンゼンスルホニルヒドラジド）などのスルホニルヒドラジド化合物、４，４’−ジフェニルスルホニルアジドなどのアジド化合物などを挙げることができ、これらは各々単独で、あるいは適宜の組み合わせによる２種以上を混合して用いてもよい。
上記の発泡剤に加え、必要に応じてステアリン酸亜鉛、亜鉛華、オクチル酸亜鉛などの亜鉛系；尿素；ほう砂；マレイン酸、フタル酸などの有機酸；ハイドロキノン；アミン類；硫黄化合物；などの発泡助剤を用いてもよく、これらも各々単独で、あるいは適宜の組み合わせによる２種以上を混合して用いてもよい。
As the blowing agent, those commonly used may be used. Specific examples thereof include nitroso compounds such as N, N-dinitrosopentamethylenetetramine, azodicarbonamide, azobisisobutyronitrile, and diazoaminobenzene. Azo compounds such as benzenesulfonyl hydrazide, sulfonyl hydrazide compounds such as 4,4′-oxybis (benzenesulfonyl hydrazide), azide compounds such as 4,4′-diphenylsulfonyl azide, and the like. Alternatively, two or more kinds in an appropriate combination may be mixed and used.
In addition to the above foaming agents, if necessary, zinc stearate, zinc white, zinc octylate, etc .; urea; borax; organic acids such as maleic acid and phthalic acid; hydroquinone; amines; sulfur compounds; These foaming aids may be used, and these may be used alone or in admixture of two or more by an appropriate combination.
発泡剤の添加量は、水添スチレン・ブタジエン共重合体とエチレン系重合体の混合体１００重量部に対し、０．１〜１０重量部、好ましくは１．５〜５重量部程度とする。
また、発泡倍率は、２〜１０倍、好ましくは３〜５倍程度とする。
発泡剤の添加量や発泡倍率が上記未満であると、柔軟性が不十分となったり、歩行感が悪くなり、上記を超えると、残留凹みが大きかったり、この凹みにより電気配線に悪影響を及ぼすことがある。
上記の発泡層の厚さは、特に限定しないが、薄すぎれば発泡層を設ける技術的効果が得られず、厚すぎてもこの効果は飽和するばかりか、発泡層による断熱効果が高くなりすぎて、ホットカーペット本体からの熱を使用者に伝達することができなくなるため、本発明では、０．５〜７ｍｍ、好ましくは１〜３ｍｍ程度が適している。
The addition amount of the foaming agent is 0.1 to 10 parts by weight, preferably about 1.5 to 5 parts by weight, with respect to 100 parts by weight of the mixture of the hydrogenated styrene / butadiene copolymer and the ethylene-based polymer.
The expansion ratio is 2 to 10 times, preferably about 3 to 5 times.
If the amount of foaming agent added or the expansion ratio is less than the above, the flexibility becomes insufficient or the walking feeling becomes worse, and if it exceeds the above, the residual dent is large, or the dent adversely affects the electrical wiring. Sometimes.
The thickness of the foam layer is not particularly limited, but if it is too thin, the technical effect of providing the foam layer cannot be obtained. If it is too thick, this effect is saturated, and the heat insulation effect by the foam layer is too high. Thus, the heat from the hot carpet body cannot be transmitted to the user, so in the present invention, about 0.5 to 7 mm, preferably about 1 to 3 mm is suitable.
また、発泡層を構成する組成物には、上記の他に必要に応じて他の添加剤を配合してもよい。
例えば、難燃性の向上を目的として炭酸カルシウム、水酸化アルミニウム、水酸化マグネシウムなどの無機充填剤；あるいは酸化チタンなどの着色剤；熱安定剤；帯電防止剤；抗菌剤；その他加工に準じて選択される滑剤などの加工性改良助剤などを挙げることができる。
Moreover, you may mix | blend another additive with the composition which comprises a foamed layer other than the above as needed.
For example, for the purpose of improving flame retardancy, inorganic fillers such as calcium carbonate, aluminum hydroxide and magnesium hydroxide; or coloring agents such as titanium oxide; thermal stabilizers; antistatic agents; antibacterial agents; Examples thereof include processability improving aids such as selected lubricants.
意匠印刷層は、上記の発泡層の上に積層される層であって、本発明のホットカーペット用表面材の意匠性を担う層である。
酢酸ビニル系、アクリル系、ウレタン系など一般に使用される極性のあるインクを用い、グラビア印刷機などの印刷機により所望の意匠を印刷する。
この際、意匠に合わせて、トリメリット酸（ＴＭＡ）、ベンゾトリアゾール（ＢＴＡ）などの発泡抑制剤を適宜添加することにより、発泡層のうち発泡抑制剤を添加して印刷された部分の発泡が抑制され、印刷する柄に同調した凹凸意匠を得ることもできる。
The design printing layer is a layer laminated on the foamed layer, and is a layer that bears the design of the surface material for hot carpet of the present invention.
A desired design is printed by a printing machine such as a gravure printing machine using a commonly used polar ink such as vinyl acetate, acrylic or urethane.
At this time, in accordance with the design, by appropriately adding a foam inhibitor such as trimellitic acid (TMA), benzotriazole (BTA), the foamed portion of the foamed layer can be foamed by adding the foam inhibitor. It is also possible to obtain an uneven design that is suppressed and synchronized with the pattern to be printed.
本発明において、透明樹脂層はホットカーペット用表面材の最上面を構成する。
透明樹脂層としては、上記の意匠印刷層に使用される印刷インクや、発泡層を構成する樹脂との接着性を考慮すると、上記の発泡層と同様の構成樹脂、すなわち水添スチレン・ブタジエン共重合体やエチレン系重合体を用いることが好ましいが、発泡層や意匠印刷層との接着性を有していれば、その他の樹脂を用いてもよいし、水添スチレン・ブタジエン共重合体を単体で用いてもよく、必要に応じて、この水添スチレン・ブタジエン共重合体よりなる透明樹脂層の表面に更にエチレン系重合体からなる層を設けてもよい。
In the present invention, the transparent resin layer constitutes the uppermost surface of the hot carpet surface material.
As the transparent resin layer, considering the adhesiveness with the printing ink used in the above-mentioned design printing layer and the resin constituting the foam layer, the same constituent resin as the above foam layer, that is, hydrogenated styrene / butadiene It is preferable to use a polymer or an ethylene-based polymer, but other resins may be used as long as they have adhesiveness with a foam layer or a design print layer, and a hydrogenated styrene / butadiene copolymer may be used. It may be used alone, and if necessary, a layer made of an ethylene polymer may be further provided on the surface of the transparent resin layer made of this hydrogenated styrene / butadiene copolymer.
透明樹脂層にも、必要に応じて熱安定剤、抗菌剤、加工性改良材を添加剤として配合してもよい。
透明樹脂層の厚さは、特に限定しないが、薄すぎれば技術的効果が得られず、厚すぎてもこの効果が飽和するため、本発明では、０．０５〜０．５ｍｍ、好ましくは０．１〜０．３ｍｍ程度が適している。
You may mix | blend a heat stabilizer, an antibacterial agent, and a workability improving material with a transparent resin layer as an additive as needed.
The thickness of the transparent resin layer is not particularly limited, but if it is too thin, a technical effect cannot be obtained, and if it is too thick, this effect is saturated. Therefore, in the present invention, 0.05 to 0.5 mm, preferably 0 .About 1 to 0.3 mm is suitable.
上記の透明樹脂層のベタつきや艶を調節する意味と、透明樹脂層を保護する意味とから、透明樹脂層の最表面には、ウレタン系、アクリル系、シリコン系などの樹脂による表面処理コート層を適宜設けることがより好ましい。 From the meaning of adjusting the stickiness and gloss of the transparent resin layer and the meaning of protecting the transparent resin layer, the surface of the transparent resin layer is a surface treatment coat layer made of a resin such as urethane, acrylic or silicon. Is more preferably provided as appropriate.
本発明のホットカーペット用表面材の最下面を構成する基材層としては、繊維質素材が好ましく用いられ、パルプ、有機繊維、ガラス繊維などを含む混抄紙などが使用でき、これらの繊維がスチレンブタジエンラテックスやアクリルエマルジョンなどによりバインディングされているものなどが好ましく用いられる。
また、必要に応じて、熱安定剤、抗菌剤などを配合したものであってもよい。
基材層の目付量は、５０〜２００ｇ／ｍ２、好ましくは８０〜１５０ｇ／ｍ２程度が適している。
As the base material layer constituting the lowermost surface of the surface material for hot carpet of the present invention, a fibrous material is preferably used, and mixed paper including pulp, organic fiber, glass fiber, etc. can be used, and these fibers are styrene. Those bound by butadiene latex or acrylic emulsion are preferably used.
Moreover, what mix | blended the heat stabilizer, the antibacterial agent, etc. may be sufficient as needed.
The basis weight of the base material layer is 50 to 200 g / m 2 , preferably about 80 to 150 g / m 2 .
本発明のホットカーペット用表面材を構成する各層は、（１）発泡剤を含有する発泡層の構成樹脂を非発泡状態で成形して発泡処方シート（後述の（５）の工程で発泡層となる）を構成し、（２）この発泡処方シートの一方の面に基材層を積層し、（３）発泡処方シートの他方の面に印刷を施して意匠印刷層を設け、（４）この意匠印刷層の上面に透明樹脂層を積層し、（５）この後、全体を加熱して発泡処方シートを発泡成形する、という手順により得ることができる。 Each layer constituting the surface material for a hot carpet according to the present invention comprises (1) a foamed layer-containing resin containing a foaming agent, molded in a non-foamed state, and a foamed prescription sheet (the foamed layer in the step (5) described later) (2) Laminating a base material layer on one side of the foam prescription sheet, (3) providing a design print layer by printing on the other side of the foam prescription sheet, (4) A transparent resin layer is laminated on the upper surface of the design printing layer, and (5) thereafter, the whole is heated to foam the foamed prescription sheet .
上記（１）の発泡処方シートの成形は、発泡剤を含有する樹脂をカレンダー加工、あるいは押出加工して、非発泡状態のシート状に成形することで行われる。
上記（２）の発泡処方シートの一方の面に基材層を積層するには、加熱による圧着（ホットラミネート）や接着剤による接着で行う。
The foamed prescription sheet (1) is formed by calendering or extruding a resin containing a foaming agent to form a non-foamed sheet.
In order to laminate the base material layer on one surface of the foamed prescription sheet of (2) above, it is carried out by pressure bonding (hot lamination) by heating or adhesion by an adhesive.
上記（３）の発泡処方シートの他の面への意匠印刷層の形成は、次のようにして行う。
通常、エチレン系重合体へ印刷を行う際は、その表面を活性化し、かつ極性を付与するために、印刷に先駆けてコロナ放電処理やプライマー処理などの前処理が必要であるが、本発明のホットカーペット用表面材を構成する発泡層(発泡処方シート）は、エチレン系重合体と共に水添スチレン・ブタジエン共重合体を用いるため、上記のような前処理を行わずに印刷を行うことができる。もちろん、前処理を行うことで更にインクの接着性能を向上することができるため、必要に応じて、前処理を行ってもよい。
The design printed layer is formed on the other surface of the foamed prescription sheet (3) as follows.
Usually, when printing on an ethylene-based polymer, pretreatment such as corona discharge treatment or primer treatment is necessary prior to printing in order to activate the surface and impart polarity. Since the foamed layer (foamed prescription sheet) constituting the surface material for hot carpet uses a hydrogenated styrene / butadiene copolymer together with an ethylene polymer, printing can be performed without the above pretreatment. . Of course, the pretreatment can further improve the ink adhesion performance. Therefore, the pretreatment may be performed as necessary.
上記（４）の意匠印刷層上に透明樹脂層を積層する方法は、熱ラミネート法などが適している。
通常、エチレン系重合体に意匠印刷層を熱ラミネートする際にも、上記と同様の前処理が必要であるが、本発明では、発泡層（発泡処方シート）として水添スチレン・ブタジエン共重合体を用いており、透明樹脂層として水添スチレン・ブタジエン共重合体を用いれば、意匠印刷層の隙間（印刷インクが載っていない箇所）の、発泡層（発泡処方シート）と透明樹脂層とが接触する箇所で、良好な接着性を確保することができるため、上記のような前処理を行わずに意匠印刷層への透明樹脂層の積層ができる。もちろん、前処理を行うことで両者の接着性能が向上するため、前処理を行ってもよい。
As a method for laminating the transparent resin layer on the design print layer (4) above, a heat laminating method or the like is suitable.
Usually, when a design printing layer is thermally laminated to an ethylene-based polymer, the same pretreatment as described above is required. However, in the present invention, a hydrogenated styrene / butadiene copolymer is used as a foamed layer (foamed prescription sheet). If a hydrogenated styrene / butadiene copolymer is used as the transparent resin layer, the foam layer (foamed prescription sheet) and the transparent resin layer in the gaps between the design print layers (where the printing ink is not placed) can be obtained. Since good adhesiveness can be ensured at the contact point, the transparent resin layer can be laminated on the design printing layer without performing the pretreatment as described above. Of course, the pretreatment may improve the adhesion performance between the two, so the pretreatment may be performed.
上記のようにして得られるホットカーペット用表面材は、表面タッチ感、リアル感、あるいは意匠性を更に向上させるために、加熱発泡成形後に凹凸ロールで型押しするメカニカルエンボスを施すこともできる。
あるいは、意匠印刷層を形成する際に、前記したように、通常の印刷インクと共に、発泡抑制剤を配合したインクを併用して印刷を行い、この発泡抑制剤配合インクによる印刷部分と接触する発泡層の部分の発泡を抑制するケミカルエンボスを行ってもよいし、このケミカルエンボスと上記のメカニカルエンボスとを組み合わせることにより、さらに意匠性や風合いの優れるものとすることもできる。
The surface material for hot carpets obtained as described above can be subjected to mechanical embossing that is embossed with a concavo-convex roll after heat-foaming molding in order to further improve the surface touch, realism, or design.
Alternatively, when forming the design print layer, as described above, the normal printing ink is used in combination with the ink containing the foam inhibitor, and the foam is brought into contact with the printing portion by the foam inhibitor-containing ink. Chemical embossing that suppresses foaming of the layer portion may be performed, or by combining this chemical embossing with the mechanical embossing, it is possible to further improve the design and texture.
本発明のホットカーペット用表面材は、防汚性に優れ、かつ優れた耐熱性、柔軟性も兼ね備えており、多種多様な意匠表現をも可能とするものである。
また、塩化ビニル樹脂や可塑剤などを使用していないため、燃焼時などにおける環境への負担や環境ホルモンなどの問題を低減することができる。
The surface material for hot carpets of the present invention is excellent in antifouling properties, has excellent heat resistance and flexibility, and can express various designs.
In addition, since no vinyl chloride resin or plasticizer is used, problems such as environmental burden and environmental hormones during combustion can be reduced.
〔実施例１〜７、比較例１，２〕
図１に示す構成のホットカーペット用表面材５を、以下の要領で製造した。
表１、表２の組成で配合した発泡層３の構成樹脂混合物を、カレンダー加工により、非発泡状態で厚さ０．４ｍｍのシート状に成形し、発泡処方シート３を得た。
この発泡処方シート３の一方の面に、接着剤を介して、目付けが９０ｇ／ｍ２のガラス／パルプ混抄紙を基材層４として積層した。
発泡処方シート３の他方の面に、グラビアインクを用い、グラビア印刷機により印刷を行い、意匠印刷層２を形成した。
なお、表１，表２中「発泡剤＊１」としては、アゾジカルボンアミドを使用した。
[Examples 1 to 7, Comparative Examples 1 and 2]
A
The constituent resin mixture of the foam layer 3 blended with the compositions shown in Tables 1 and 2 was formed into a 0.4 mm-thick sheet in a non-foamed state by calendering to obtain a foam prescription sheet 3.
A glass / pulp mixed paper having a basis weight of 90 g / m 2 was laminated as a base material layer 4 on one surface of the foamed prescription sheet 3 through an adhesive.
The design printing layer 2 was formed on the other surface of the foam prescription sheet 3 by using a gravure ink and printing with a gravure printing machine.
In Tables 1 and 2, azodicarbonamide was used as the “foaming agent * 1”.
意匠印刷層２の上面に、片面にウレタン系塗料が数μｍ塗布されたＥＶＡ／ポリエチレンの混合物からなる０．２ｍｍ厚さの透明フィルムを透明樹脂層１として熱ラミネートにより積層した。 On the upper surface of the design printing layer 2, a 0.2 mm thick transparent film made of an EVA / polyethylene mixture coated with several μm of urethane-based paint on one side was laminated as a transparent resin layer 1 by thermal lamination.
最後に、加熱発泡炉にて、上記の積層シートを加熱し、発泡層３の発泡倍率が３倍になるように発泡して、本発明および比較のホットカーペット用表面材５を得た。
Finally, the above laminated sheet was heated in a heating foaming furnace and foamed so that the foaming ratio of the foamed layer 3 was three times to obtain the
〔比較例３〕
発泡層３の構成樹脂を、エチレン・酢酸ビニル共重合体（ＶＡ２５％）８０重量部、メタロセン触媒使用ポリエチレン樹脂２０重量部とした以外は実施例１と同様にしてホットカーペット用表面材を得た。
[Comparative Example 3]
A surface material for a hot carpet was obtained in the same manner as in Example 1 except that the constituent resin of the foam layer 3 was 80 parts by weight of an ethylene / vinyl acetate copolymer (VA 25%) and 20 parts by weight of a polyethylene resin using a metallocene catalyst. .
実施例１〜７、比較例１〜３により得られたホットカーペット用表面材について、次の要領・基準による発泡性、熱変形性、加工性の評価を行い、結果を表３に示す。 The surface materials for hot carpets obtained in Examples 1 to 7 and Comparative Examples 1 to 3 were evaluated for foamability, thermal deformability, and workability according to the following points and standards, and the results are shown in Table 3.
（１）発泡性：加熱発泡の際における発泡セルの状態と、目標の発泡倍率達成度による評価。
◎：発泡セルが良好で、目的とする発泡倍率が得られる。
○：発泡セルは良好であるが、発泡倍率が若干未達
△：発泡セルが若干不良で、発泡倍率も若干未達
×：発泡セルが不良で、発泡倍率も未達
（２）熱変形性：８０℃の恒温槽において７２時間放置した後の変形を観察。
◎：変形しない
○：変形するが目立たない
△：変形し、やや目立つ
×：変形し、形状を保てない
（３）加工性：カレンダー加工で、混練り加工ができるかと、積層が良好に行えるかについての評価。
○：良好
△：やや問題あり
×：不良
(1) Foaming property: Evaluation based on the state of the foamed cell during heat foaming and the target achievement of the foaming ratio.
(Double-circle): A foam cell is favorable and the target foaming magnification is obtained.
○: Foamed cell is good, but expansion ratio is slightly less than △: Foam cell is slightly poor, expansion ratio is also slightly unsatisfactory ×: Foam cell is poor, and expansion ratio is not achieved (2) Thermal deformation : Observation of deformation after standing in a thermostat at 80 ° C. for 72 hours.
◎: Not deformed ○: Deformed but not conspicuous △: Deformed and slightly conspicuous ×: Deformed and unable to maintain shape (3) Workability: Whether the kneading process can be performed by calendering or good lamination Evaluation about.
○: Good △: Somewhat problematic ×: Poor
本発明のホットカーペット用表面材は、電気機器であるホットカーペットの上面に敷くことにより、特にキッチンやダイニングにおける食物、飲料、調味料などのこぼし汚れなどの除去を容易にすることができる。
また、耐熱性や柔軟性を必要とするその他の電気機器用部材、自動車などの車輌用部材、建築用部材などにも用いることができる。
The surface material for a hot carpet of the present invention can easily remove spilled dirt such as food, beverages, seasonings and the like particularly in a kitchen or dining room by laying on the upper surface of a hot carpet that is an electric device.
Moreover, it can be used for other members for electric equipment that require heat resistance and flexibility, members for vehicles such as automobiles, and members for construction.
１ 透明樹脂層
２ 意匠印刷層
３ 発泡層
４ 基材層
５ ホットカーペット用表面材
DESCRIPTION OF SYMBOLS 1 Transparent resin layer 2 Design printing layer 3 Foam layer 4
Claims (3)
前記発泡層が、水添スチレン・ブタジエン共重合体５０〜８０重量％とエチレン系重合体５０〜２０重量％との混合体を非架橋で発泡させた層であることを特徴とするホットカーペット用表面材。 In order from the bottom, in the surface material for hot carpet in which the base material layer, the foam layer, the design printing layer, and the transparent resin layer are provided,
The foamed layer is a layer obtained by foaming a mixture of hydrogenated styrene / butadiene copolymer 50 to 80% by weight and ethylene polymer 50 to 20% by weight in a non-crosslinked manner. Surface material.
（２）非発泡状態の樹脂層の一方の面に基材層を積層する工程、
（３）非発泡状態の樹脂層の他方の面に印刷を施して意匠印刷層を設ける工程、
（４）意匠印刷層の上面に透明樹脂層を積層する工程、
（５）加熱して非発泡状態の樹脂層を発泡成形する工程、
からなることを特徴とする請求項１または２に記載のホットカーペット用表面材の製造方法。 (1) The constituent resin of the foam layer containing the foaming agent is a mixture of hydrogenated styrene / butadiene copolymer 50 to 80% by weight and ethylene polymer 50 to 20% by weight, in a non-crosslinked and non-foamed state Forming a resin layer by molding,
(2) a step of laminating a base material layer on one surface of the non-foamed resin layer,
(3) A step of printing on the other surface of the non-foamed resin layer to provide a design print layer,
(4) A step of laminating a transparent resin layer on the upper surface of the design print layer,
(5) A step of foaming a non-foamed resin layer by heating,
The manufacturing method of the surface material for hot carpets of Claim 1 or 2 characterized by the above-mentioned.
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| JP2003394983A JP4451643B2 (en) | 2003-11-26 | 2003-11-26 | Surface material for hot carpet and manufacturing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2003394983A JP4451643B2 (en) | 2003-11-26 | 2003-11-26 | Surface material for hot carpet and manufacturing method thereof |
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| JP2005153303A JP2005153303A (en) | 2005-06-16 |
| JP4451643B2 true JP4451643B2 (en) | 2010-04-14 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101766431A (en) * | 2010-02-11 | 2010-07-07 | 冯德强 | digital carpet |
| CN102715821A (en) * | 2012-07-03 | 2012-10-10 | 太仓高腾复合材料有限公司 | Waterproof and moistureproof carpet and manufacture method thereof |
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